JP3148960B2 - Photo cyan coupler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coupler used as a material for a silver halide color photographic light-sensitive material, and more particularly to a novel coupler capable of forming a dye image having excellent color reproducibility and fastness to heat and humidity. The present invention relates to a photographic cyan coupler.

[0002]

2. Description of the Related Art In general, when a color photograph is produced, a silver halide color photographic light-sensitive material is exposed to light and then subjected to a color development process. The amine color developing agent reacts with the dye-forming coupler to form a dye and form a color image.In such a photographic method, a color reproduction method using a subtractive color method is used, whereby yellow, magenta and cyan are used. Are formed.

Conventionally, photographic couplers used for forming the yellow image include, for example, acylacetanilide couplers, and magenta image forming couplers include, for example, pyrazolone and pyrazolobenzimidazole. Pyrazolotriazole or indazolone couplers are known, and as a coupler for cyan image formation, for example, phenol or naphthol couplers are generally used,
It is desired that the dye images obtained from these couplers do not discolor even if exposed to light for a long time or stored under high temperature and high humidity.

However, as couplers for forming cyan dyes, the above-mentioned phenol couplers and naphthol couplers, which have been studied and put to practical use, have a spectral absorption characteristic of a formed cyan dye image.
Various other proposals have hitherto been made, including the selection and exploration of substituents in couplers, with the aim of improving heat resistance and moisture resistance. No coupler has yet been found that satisfies all requirements.

Accordingly, the present inventors have further studied in view of such a situation, and as a result, it has been found that a cyan dye image formed can form a dye image having excellent spectral absorption characteristics, heat resistance and moisture resistance. I found a coupler.

[0006]

Accordingly, it is a first object of the present invention to provide a novel photographic cyan coupler which can be used as a material for a silver halide color photographic light-sensitive material. An object of the present invention is to provide a photographic cyan coupler capable of forming a dye image having excellent spectral absorption characteristics, heat resistance and moisture resistance of the formed cyan dye image.

[0007]

The above object of the present invention is achieved by the following constitution.

A photographic cyan coupler represented by the general formula [I] or [II].

[0009]

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In the formula, R represents a substituent, and m represents 0 or 1.
Represents an integer of 5 to 5, and n represents 0 or an integer of 1 to 3.
When m or n is an integer of 2 or more, a plurality of Rs may be the same or different. R ₁ is an aliphatic group which may have a substituent, an aryl group, a heterocyclic group, an aliphatic oxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group,
A carbamoyloxy group, a phosphonyloxy group, a carbamoyl group, a sulfamoyl group, an amino group, an acylamino group, an imide group, a sulfonamide group, a sulfamoylamino group, an oxycarbonylamino group, and a phosphonylamino group, and X represents a hydrogen atom Alternatively, it represents a group which is released by a reaction with an oxidized form of a color developing agent.

Hereinafter, the present invention will be described more specifically.

In the general formulas [I] and [II], the substituent represented by R is not particularly limited, but is typically an aliphatic, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, Examples include alkenyl, cycloalkyl and the like.Other than these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, each group such as heterocyclic thio, And spiro compound residues, bridged hydrocarbon compound residues, and the like.

Hereinafter, the present invention will be described in more detail. The aliphatic group represented by R may be linear or branched, and may be saturated or unsaturated. The aliphatic group may be substituted with another substituent, and the substituent is not particularly limited, but typically, aryl, anilino,
Examples include acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl,
Alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, Examples include groups such as aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, and heterocyclic thio, as well as spiro compound residues and bridged hydrocarbon compound residues.

As the aryl group, a phenyl group, a 1-naphthyl group and a 2-naphthyl group are preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include linear and branched alkyl groups, phenyl groups, 1-naphthyl groups and 2-naphthyl groups, which are further substituted with other substituents. It may be.

The alkenyl group may have 2 to 3 carbon atoms.
2, the cycloalkyl group has 3 to 3 carbon atoms.
12, preferably 5 to 7, and the alkenyl group may be linear or branched.

The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group. Examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group. Examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group, and an aryloxyphosphonyl group. Group,
Arylphosphonyl group, etc .; acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group An acyloxy group such as an alkylcarbonyloxy group or an arylcarbonyloxy group; a carbamoyloxy group such as an alkylcarbamoyloxy group or an arylcarbamoyloxy group; a ureido group such as an alkylureido group or an arylureido group; Examples of the famoylamino group include an alkylsulfamoylamino group, an arylsulfamoylamino group, and the like;
2-membered groups are preferred, specifically, 2-furyl group, 2-thienyl group, 2-pyrimidyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, a 5- to 7-membered heterocyclic oxy group is preferred, 3, 4, 5, 6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable. Pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5
-Triazine-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutar Imido group and the like; spiro compound residues such as spiro [3.3] heptane-1-yl and the like; bridged hydrocarbon compound residues as bicyclo [2.2.1] heptane-1-yl and tricyclo [ 3.3.1.1 ^3.7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Heptane-1-yl and the like.

In the general formula [I], specific examples of the aliphatic group represented by R ₁ include the same groups as the above-mentioned aliphatic group for R.

Specific examples of the aryl group represented by R ₁ include the same groups as the above-mentioned substituents of the R aliphatic group.

Specific examples of the heterocyclic group represented by R ₁ include the same groups as those described above for the substituent of the R aliphatic group.

An aliphatic oxy group represented by R ₁ ,
Specific examples of the aryl of the aryloxy group, the heterocycle of the heterocyclic oxy group, the acyl of the acyloxy group, and the carbamoyl of the carbamoyloxy group include the same groups as the above-mentioned substituents for the aliphatic group for R.

Specific examples of the phosphonyloxy group represented by R ₁ include an alkylphosphonyloxy group, an arylphosphonyloxy group, an alkyloxyphosphonyloxy group, and an aryloxyphosphonyloxy group.

Examples of the carbamoyl group and sulfamoyl group represented by R ₁ include the same groups as the above-mentioned substituents for the aliphatic group represented by R.

The amino group represented by R ₁ may have a substituent, and specific examples include an alkyl group and a phenyl group.

Specific examples of the acylamino group, imide group, sulfonamide group and sulfamoylamino group represented by R ₁ include the same groups as the above-mentioned substituents for the aliphatic group for R.

Examples of the oxycarbonylamino group represented by R ₁ include an alkyloxycarbonylamino group and a phenyloxycarbonylamino group.
Specific examples of the phosphonylamino group include an alkylphosphonylamino group, an arylphosphonylamino group, an alkyloxyphosphonylamino group, and an aryloxyphosphonylamino group.

R is preferably aliphatic, aryl,
Acylamino, sulfonamide, halogen atom, acyl, carbamoyl, sulfamoyl, alkoxy, acyloxy, carbamoyloxy, imide, ureido, sulfamoylamino, carbamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Examples include alkoxycarbonyl, aryloxycarbonyl, and hydroxy groups.

Preferred examples of R ₁ include aliphatic, aryl, aliphatic oxy, acylamino, imide, sulfonamide, sulfamoylamino, carbamoylamino, oxycarbonylamino and phosphonylamino groups.

The group capable of leaving by reacting with the oxidized form of the color developing agent represented by X includes, for example, a halogen atom (a chlorine atom, a bromine atom, a bromine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heteroatom linked by N atom ring,
Alkyloxycarbonylamino, aryloxycarbonylamino, each group such as carboxyl,
Preferably halogen atom, especially chlorine atom, alkoxy,
Aryloxy, alkylthio and arylthio groups.

Hereinafter, typical specific examples of the cyan coupler of the present invention will be shown, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The compound represented by the above general formula [I] or [I] according to the present invention.
I] is a cyan coupler represented by Journal of American Chemical Society (J. Am. Chem. S)
oc.), 65, 1804 (1943), Jurnal Organicheskoy Himier (Zh. Org. Khim.), 14 (5), 1051 (1978), and can be easily synthesized by those skilled in the art.

The following are examples of the synthesis of the compounds of the present invention.

The synthesis route is as follows.

[0042]

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I) Synthesis of Exemplified Compound (8) 18 g of Intermediate (I) (synthesized according to the synthesis method described in J. Am. Chem. Soc., 65, 1804 (1943)) was dissolved in 200 ml of pyridine. Thereafter, the mixture was stirred at 10 ° C. To this was added 36 g of intermediate (II) over about 2 hours. After the addition was completed, the mixture was further stirred for 2 hours. The reaction solution was poured into 500 ml of water and extracted with 400 ml of ethyl acetate. After washing twice with water, the extract was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a pale orange oily compound. This was purified by column chromatography to obtain 39 g (yield 78%) of Exemplified Compound (8) as a pale yellow oily compound.
(Identification was performed by ¹ H, NMR, IR, and FD mass spectra).

II) Synthesis of Exemplified Compound (17) 13 g of Intermediate (III) (synthesized according to the synthesis method described in Zh. Org. Khim., 14 (5), 1051 (1978)) was added to 150 ml of pyridine. After dissolution, 36 g of intermediate (II) was added over 2 hours while stirring at 10 ° C. After the addition was completed, the mixture was further stirred for 2 hours. The reaction solution was poured into 500 ml of water, and the precipitated crystals were collected by filtration and then recrystallized with 80% ethanol to give an exemplary compound (1) which was an off-white solid compound.
7) (29 g, yield 70%, melting point: 158 ° C.) was obtained (identification was performed by ¹ H-NMR, IR and FD mass spectra).

III) Synthesis of Exemplified Compound (18) 13 g of Intermediate (III) (synthesized according to the synthesis method described in Zh. Org. Khim., 14 (5), 1051 (1978)) was converted to pyridine 15
After dissolving in 0 ml, while stirring at 10 ° C., 27 g of the intermediate (IV) was added over 2 hours. After the addition,
The mixture was further stirred for 2 hours. Pour the reaction solution into 500 ml of water,
Extracted with 400 ml of ethyl acetate. After washing twice with water, it was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a brown oily compound. This was purified by column chromatography to give 24.5 g of Compound (18), which is a pale orange oily compound (yield: 68).
%) (Identification was performed by ¹ H-NMR, IR and FD mass spectra).

The coupler of the present invention is generally used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 mol per mol of silver halide.
It can be used in a range of × 10 ^-1 mol.

The coupler of the present invention can be used in combination with another type of cyan coupler. The methods and techniques used in conventional dye-forming couplers are similarly applied to the couplers of the present invention.

The coupler of the present invention can be used as a material for forming a color photograph by any coloring method, and specific examples thereof include an external coloring method and an inner coloring method.
When used as an external color developing method, the coupler of the present invention can be used by dissolving it in an aqueous alkali solution or an organic solvent (eg, alcohol) and adding it to a developing solution.

When the coupler of the present invention is used as a material for forming a color photograph by an internal color developing method, the coupler of the present invention is used by being contained in a photographic light-sensitive material.

Typically, a method in which the coupler of the present invention is blended with a silver halide emulsion and this emulsion is coated on a support to form a color photographic material is preferably used. The coupler of the present invention is used, for example, for color photographic light-sensitive materials such as color negative and positive films and color photographic paper.

The light-sensitive material using the coupler of the present invention such as the color photographic paper may be of a single color or a multicolor. In a multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but is usually contained in a red-sensitive silver halide emulsion layer. The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of three primary color regions of the spectrum. Each structural unit can be composed of a single layer or multiple emulsion layers sensitive to certain regions of the spectrum. The constituent layers of the light-sensitive material, including the layers of the image forming constituent units, can be arranged in various orders as known in the art. A typical multicolor light-sensitive material is a cyan dye image-forming structural unit comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers is a cyan coupler of the present invention). Magenta dye image-forming units comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion containing at least one yellow coupler It consists of a yellow dye image forming structural unit comprising a layer carried on a support.

The light-sensitive material can have additional layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer and the like. The coupler of the present invention may be incorporated into an emulsion according to a conventionally known method. For example, the coupler of the present invention may be added to a high-boiling organic solvent having a boiling point of 175 ° C. or more, such as tricresyl phosphate or dibutyl phthalate, or a low-boiling solvent such as butyl acetate or butyl propionate alone or, if necessary, a mixture thereof. Is dissolved alone or in combination, then mixed with a gelatin aqueous solution containing a surfactant, and then emulsified by a high-speed rotary mixer or a colloid mill, and then added to silver halide to be used in the present invention. The silver emulsion can be adjusted.

The silver halide composition preferably used in the light-sensitive material using the coupler of the present invention includes silver chloride, silver chlorobromide or silver chloroiodobromide. Further, a combination mixture such as a mixture of silver chloride and silver bromide may be used. That is,
When a silver halide emulsion is used for color printing paper, particularly fast developability is required, so that the silver halide composition preferably contains a chlorine atom as a silver halide composition and contains at least 1% silver chloride. Silver chloride, silver chlorobromide or silver chloroiodobromide.

The silver halide emulsion is chemically sensitized by a conventional method. Also, it can be optically sensitized to a desired wavelength range.

In the photographic industry, a silver halide emulsion is used to prevent fogging during the production process, storage, or photographic processing of a light-sensitive material, and / or to stably maintain photographic performance. Compounds known as agents can be added.

The color light-sensitive material using the coupler of the present invention includes a color fogging inhibitor, a dye image stabilizer, an ultraviolet absorber, an antistatic agent, a matting agent, which are usually used in light-sensitive materials.
Surfactants and the like can be used. These are discussed, for example, in Research Disclosure
sure), Volume 176, pp. 22-31 (December 1978).

The color photographic light-sensitive material using the coupler of the present invention can form an image by performing a color development process known in the art.

The color photographic light-sensitive material using the coupler according to the present invention contains a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and can be processed by an alkaline activating bath. it can.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleaching and fixing after color development.
The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0061]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side, and a red photosensitive color photosensitive material sample 1 was prepared. Unless otherwise specified, the amount of the compound to be added is represented per 1 m ² (silver halide is calculated as silver).

First layer: emulsion layer 1.3 g gelatin, red-sensitive silver chlorobromide emulsion (99.5 silver chloride)
0.21 g) and 0.2 g of dioctyl phthalate.
9.1 g of comparative cyan coupler (a) dissolved in 45 g
Red-sensitive emulsion layer consisting of 10 ^-4 mol.

Second layer: protective layer A protective layer containing 0.50 g of gelatin. In addition, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardening agent so as to be 0.017 g per 1 g of gelatin.

Next, Sample 2 of the present invention was prepared in exactly the same manner as in Sample 1 except that the comparative cyan coupler (a) was replaced with the following coupler (the amount added was the same molar amount as that of the comparative cyan coupler (a)). ~ 8 were created.

Each of the samples 1 to 8 obtained above was subjected to wedge exposure according to a conventional method, and then subjected to development processing in the following step.

The processing conditions are as follows.

Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleaching Fix 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds [Color developing solution] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5.0 g Potassium bromide 0.02 g Potassium chloride 2.0 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-diphosphonic acid disodium 1.0 g Diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water was added to make the total volume 1 liter, Adjusted to 0.10.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 00 ml Ammonium sulfite (40% solution) 27.5 ml Water was added to adjust the total amount to 1 l. And adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing Solution] 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene- 1,1-diphosphonic acid 2.0 g O-phenylphenol sodium 1.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g fluorescent whitening agent (4,4′-diaminostilbene disulfonic acid derivative) 1.5 g water is added to bring the total volume to 1 l, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The concentration of each of the processed samples 1 to 8 was measured using a densitometer (model KD-7, manufactured by Konica Corporation).
(C, 80% RH) atmosphere for 14 days to examine the heat resistance and humidity resistance of the dye image.

The results are shown below. However, the heat resistance and humidity are represented by the percentage of the dye remaining after the heat resistance and humidity test with respect to the initial concentration of 1.0.

The comparative cyan coupler (a) is shown below.

[0074]

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Sample No. Coupler used Heat / moisture resistance, residual dye ratio (%) 1 Comparison (a) 61 2 Invention (8) 893 Invention (9) 874 Invention (12) 905 Invention (13) 92 6 Invention (14) 887 The present invention (19) 868 The present invention (21) 89 As is clear from the above results, any of the samples using the coupler of the present invention was compared with the sample using the comparative coupler. It can be seen that the dye remaining ratio is high, the heat resistance and the moisture resistance are excellent, and the solidity is high.

Example 2 The following layers were sequentially coated on a subbed triacetyl cellulose film support from the support side, and a red light-sensitive color reversal light-sensitive material containing the following couplers (Samples 9 to 14) )created.

First layer: emulsion layer 1.4 g of gelatin shown in Table 3, dissolved in 1.4 g of gelatin, 0.5 g of a red-sensitive silver chlorobromide emulsion (containing 96 mol% of silver chloride) and 1.5 g of dibutyl phthalate. × 10 ^-4 mol of a red-sensitive emulsion layer.

Second layer: protective layer A protective layer containing 0.5 g of gelatin. In addition, 2, as a hardener
4-Dichloro-6-hydroxy-s-triazine sodium salt was added at 0.017 g / g of gelatin.

Each of the samples obtained above was subjected to wedge exposure according to a conventional method, and then subjected to development processing in the next step.

[Reversal Processing Step] Processing Step Temperature Time First development 38 ° C. 6 minutes Rinse 38 ° C. 2 minutes Inversion 38 ° C. 2 minutes Color development 38 ° C. 6 minutes Adjustment 38 ° C. 2 minutes Bleaching 38 ° C. 6 minutes Constant Attached 38 ° C for 4 minutes Rinse with water 38 ° C for 4 minutes Stable Room temperature 1 minute Drying The composition of the treatment liquid is as follows.

[First developer] Sodium tetrapolyphosphate 2.0 g Sodium sulfite 20.0 g Hydroquinone monosulfonate 30.0 g Sodium carbonate (monohydrate) 30.0 g 1-phenyl-4-methyl-4-hydroxymethyl- 3-Pyrazolidone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water to make 1000 ml.

[Inverting solution] Nitrilotrimethylenephosphonic acid hexasodium salt 3.0 g Stannous chloride (dihydrate) 1.0 g p-aminophenol 0.1 g Sodium hydroxide 5.0 g Glacial acetic acid 15 ml Water was added. To 1000 ml.

[Color developing solution] Sodium tetrapolyphosphate 2.0 g Sodium sulfite 7.0 g Sodium tertiary phosphate (12 hydrate) 36.0 g Potassium bromide 1.0 g Potassium iodide (0.1% solution) 90 ml Hydroxide Sodium 3.0 g Citrazinic acid 1.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 11.0 g Ethylenediamine 3.0 g Water is added to make up to 1000 ml.

[Preparation Solution] Sodium sulfite 12.0 g Sodium ethylenediaminetetraacetate (dihydrate) 8.0 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water is added to make 1000 ml.

[Bleaching solution] Sodium ethylenediaminetetraacetate (dihydrate) 2.0 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120.0 g Potassium bromide 100.0 g Water is added to make up to 1000 ml.

[Set solution] Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to make up to 1000 ml.

[Stabilizing solution] Formalin (37% by weight) 5 ml KONIDAX (manufactured by Konica Corporation) 5 ml Add water to make 1000 ml.

For each of the samples treated as described above, the heat resistance and moisture resistance of the dye image were examined in the same manner as in Example 1. The results are shown below.

Sample No. Coupler used Heat / moisture resistance, dye residual ratio (%) 9 Comparison (a) 59 10 Invention (4) 87 11 Invention (10) 89 12 Invention (13) 90 13 Invention (22) 86 14 Invention (27) 88 As is clear from the above results, all of the samples using the coupler of the present invention have a higher dye residual ratio and are excellent in heat resistance and moisture resistance as compared with the samples using the comparative coupler. It turns out that it is robust.

Example 3 On a transparent polyethylene terephthalate film support,
The photothermographic layer comprising a support 1 m ² per following components was coated to create a photothermographic material.

Silver benztriazole 0.6 g gelatin 3.0 g reducing agent * ¹ 0.97 g coupler (18) of the present invention 1.0 g silver iodobromide (in terms of silver) 0.45 g polyvinylpyrrolidone 1.0 g benzotriazole 0.4 g 02g Inhibitor * ² 0.001g Hot solvent * ³ 4.5g

[0092]

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After imagewise exposing the above photosensitive material, it was superposed on an image receiving material obtained by coating polyvinyl chloride on photographic baryta paper and thermally developed at 150 ° C. for 1 minute. A cyan transfer image was obtained.

Example 4 FIG. 1 shows the spectral absorption spectra (solvents) of the azomethine dye (D-1) obtained from the coupler (8) of the present invention and the indoaniline dye (D-2) obtained from the comparative coupler (a). FIG. 1 is a dye (D-
1) shows a spectral absorption curve of the dye (D-2), and 2 shows a spectral absorption curve of the dye (D-2). The vertical axis represents absorbance and the horizontal axis represents wavelength.

As is evident from FIG. 1, the dye (D-1) obtained from the coupler of the present invention achieves a reduction in the side absorption at 400 to 500 nm and a sharpening of the main absorption.

[0096]

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[0097]

The cyan dye image formed from the cyan coupler according to the present invention has excellent spectral absorption characteristics, is robust against heat and humidity, and the coupler is also effective as a dye-providing substance in a photothermographic material. is there.

[Brief description of the drawings]

FIG. 1 is a diagram showing a spectral absorption spectrum of a dye.

[Explanation of symbols]

 1 Spectral absorption curve of dye (D-1) 2 Spectral absorption curve of dye (D-2)

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/38

Claims (1)

(57) [Claims] 1. A photographic cyan coupler represented by the general formula [I] or [II]. Embedded image [Wherein, R represents a substituent, m represents 0 or an integer of 1 to 5, and n represents 0 or an integer of 1 to 3. m or n
Is an integer of 2 or more, a plurality of Rs may be the same or different. R ₁ is an optionally substituted aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, phosphonyloxy group, carbamoyl group ,
Represents a sulfamoyl group, an amino group, an acylamino group, an imide group, a sulfonamide group, a sulfamoylamino group, an oxycarbonylamino group, and a phosphonylamino group;
X represents a hydrogen atom or a group which is released by a reaction with an oxidized form of a color developing agent. ]